Process for making phthalocyanines containing-sh groups



Patented Feb. 25, I94;

UNITED TATES A N OFFICE PROCESS FOR MAKING PHTHALOCYANINES CONTAINING -SH GROUPS Norman Hulton Haddock and Clifford Wood, Blackley, Manchester, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No' Drawinga Application June 21, 1944, Serial No. 541,455. In Great Britain July 7, 1943 V 6 Claims.

The present invention relates to the manufacture of new dyestufis and more particularly to the manufacture of. new sulphur-containing dyestuffs; 1 a I We have found that when a copper phthalo-- eyani-ne tetra-(4)-sulphonyl chloride is heated with benzyl mercaptan, the colour of the mixture, which is blue, changes to green and water and hydrogen chloride are evolved. From the product dibenzyl disulphide can be extracted with alcohol, a bright green residue being left. This green residue will dissolve in dilute sodium hydroxide solution which has previously .been' boiled with a trace of sodium sulphide to remove dissolved oxygen. Accordingly the reaction which takes place may be regarded as the reduction of the copper phthalocyanine tetra-(4)- sulphonyl chloride to the corresponding mercaptan by the benzyl mercaptan, the latter becoming itself simultaneously oxidised to dibenzyl disulphide. This statement is however only to be considered as a theory which may or may not be correct. The aforesaidbright green residue, which is possibly therefore copper tetra- (4) -mercaptophth'alocyanine, will dissolve also in aqueous sodium sulphide solution to give a bluish grey solution of similar appearance to that obtained by dissolving it in sodium hydroxide solution. When the solution in either of these solventsis applied to cotton fabric, the latter assumes a greyish hue, which is converted by atmospheric oxidation to bright green. The

green product referred to behaves in a similar manner to a sulphur dyestufi inasmuch as it dis solves in aqueous sodium sulphide, yielding a solution which can be used for dyeing by the customary technique employed in connection.

with. sulphur dyestufls. In place of copper phthalocyanine tetra (4) sulphonyl chloride other phthalocyanine sulphonyl chlorides may be used; likewise the benzyl mercaptan can be rein the present invention besides benzyl mercaptan, also p-thiocresol, thio-B-naphthol, 2-mer-' capto-benzthiazole, m-dimercaptobenzene and 4- mercaptophthalic anhydride, for instance. It will be noted that all the aforegoing mercaptans are either liquid or melt to form liquids at the temperature of the reaction. The latter, as will wet treatment.

The following examples in which the parts are by weight illustrate, but do not limit, the invention.

Example 1 aircproduce bright green dyeings of good fast ness to washing, soap boiling, chemick and light.

In place of the 50 parts of benzyl mercaptan used above, there are employed with similar results 50 parts of 2-mercaptobenthiazole.

Example 2 5 parts of copper phthalocyanine tetra-(4)- sulphonyl chloride, obtainable as described in Example 1, are heated with 25 parts of p-thiocresol at 170-175 C. for 2 hours. The melt is diluted with parts of alcoho1 and the green sediment filtered off and Washed with 300 parts of alcohol. The product after drying is a bright green powder which dissolves in hot dilute aqueous sodium sulphide solution, giving a bluish grey solution from which cotton is dyed in grey or black shades, which oxidise in air to bright green.

Example 3 5 parts of metal-free phthalocyanine trisulphonyl chloride (obtainable by heating with phosphorus pentachloride in nitrobenzene trisodium metal free phthalocyanine trisulphonate,

3 itself got by sulphonating metal-free phthalocyanine), are heated with parts of benzyl mercaptan at 170-1'75 C. for 2 hours. The mixture is cooled to C., diluted with parts of a1- cohol, filtered and the residue washed with 500 parts of hotalcoholandfinallywith water. w'Ihe bright yellowish green product dissolves .in *hot dilute sodium sulphide solution, giving a bluish grey solution from which cotton is dyed in grey.

shades, which oxidises in air to bright yellowish green.

Example i 4 9 parts of metal-free phthalocyanine ,trisulphonyl chloride (obtainable as de'serbiedZiniEX- ample 3) are heated with '60 parts of dodecyl mercaptan at 175-180 C. for 1 hour. The mixture, which'is' green, is cooled :to \80 LC. and diluted with 200 parts of benzene. The suspension is filtered and the filter-cake washed three times with 50 parts of benzene and dried. A new dyestufi, which dyes cotton similarly to that ofExample'3;is"obtained.

Example .5

-10 parts of metal-free phthalocyanine trisulp'honyl chloride --(obtainable as-described in Example 39 are heated with'50 parts of m-dimercaptobenzene at --l25''C. for A hour. "The green mixtureis cooled to "80 Grand diluted with 200 parts of alcohol. The suspension is filtered, and the filter-cake washed three times with parts of alcohoL-anddried. A new dyestufi which dyes cotton similarly -to that of Example 3 is obtained. I

-We'claim': I 1. Process, for "the 'manufacture of sulphur containing dyestuffs of the phthalccyanineseries,

which comprisesheating, ;at a temperature of at least 120 C., aphthalocyanine compound selected from the group consisting of 'metal- :and metalfree phthalocyanines containing sulph'onyl-ch-loride groups, with an organic mercaptan which is liguid at the selected reaction temperature, until the sulphonyl-chloride groups of the original phthalocyani'ne compound have been converted into mercapto groups. v

2. Process for the -manufacture of sulphur containing dyestuffs of the phthalocyariine series, which comprises heating, at a temperature between 120 and 180 0,, a -phthalocyanine compound selected from the group consisting of metalandmetal-fre'e 'phthaloc'yanines containing 'sulphonyl-chloride groups, with an organic mercaptan which "is liquid at the :-reaction "tem- 7' -:ors zthe zphthalocyanine series, which com- :prises heating atatemperature of 120 to 180 C., a metal-free phthalocyanine polysulphonyl chloride with an organicmercaptan which is liquid at the reactionitemperature, until the sulphonylchloride groups of the original phthalocyanine compound have been converted into mercapto groups. 7

:Processifor.thermanufacture of sulfur colors of the phthalocyanine series, which comprises heating metal-"freephthalocyani'ne-trisulphonyl chloride with benzyl mercaptan at a temperature of about to 0., and recovering from the reaction mass aphthalocyanine-coloring mat,-

ter which is soluble in aqueous sodiumsulfide and inaqueous-sodiumhydroxide. I

6. Process for the'manufacture of-su1fur1colors of the phthalocyanine series, which comprises heating metalfree-phthalocyanine-trisulphonyl chloride with dodecyl =mercaptan at a 'temperae' ture-of about 175 to '180G., and recovering gfrom the-reaction mass a phthalocyanine coloring matter which is Soluble queous sodium sulfide and hytiroxide.

' NORMAN HULTON HADDGCK.

CLIFFORD' WOOD.

EREFERENGES CIT-ED "The ,ifollowing references ,are of record in :the

file of this patent:

UNITED :smrns :BATEN'IYS Number Name fDate 2 ,1'821763 Muehlbauer Dec. 5, "1939' -2 ,-21.9;3,30 Madler et a1 0.ct.'29,1i940 2,342,662 :Haddock "Feb. .29, 1 944 FOREIGN PATENTS Number Country Date 492,1 7"! British sept rai eaa 

